JP5928334B2 - Laminated film and molded body - Google Patents

Description

  The present invention relates to a laminated film. The present invention particularly relates to a laminated film which is excellent in molding followability and scratch resistance as a molding material and is advantageous in terms of productivity and cost.

  A molding material such as decorative molding is provided with a surface hardness layer in order to prevent scratches during molding and to prevent scratches in the process of using the article after molding. However, the surface-hardened layer does not have enough elongation to follow the molding, and therefore cracks occur during molding. In extreme cases, the film breaks and the surface hardened layer peels off. For this reason, means such as forming a surface hardened layer after molding, or completely curing by heating or energy ray irradiation after molding in a semi-cured state is applied.

  Since the article after molding is processed three-dimensionally, it is very difficult to provide a surface hardened layer by post-processing. Further, when molding in a semi-cured state, the mold may be soiled depending on molding conditions. Therefore, as a scratch-resistant material that follows molding, a “self-healing material” that self-repairs minor scratches from the prevention of scratches due to increased hardness has recently attracted attention. Self-healing materials are capable of self-healing deformation in their own elastic recovery range (this property is called self-healing), and two types are widely known: thermosetting type and energy ray curable type using ultraviolet rays and electron beams. ing. Patent Document 1 describes an energy beam curable material having a high surface hardness. Patent Documents 2 and 3 describe self-healing energy beam curable materials. Patent Document 4 describes a self-healing thermosetting material.

JP 2009-84395 A Japanese Patent Laid-Open No. 2004-35599 JP 2006-137780 A International Publication No. WO2011 / 136042 Pamphlet

  However, the energy beam curable material described in Patent Document 1 has a problem that it has a high surface hardness but does not have self-healing properties and is not suitable for molding applications with a high molding magnification because of its low elongation.

  The energy ray curable materials described in Patent Documents 2 and 3 and the thermosetting material described in Patent Document 4 have sufficient self-healing properties, but dioctyl phthalate derived from a PVC sheet, cosmetics, oily magic, etc. In some cases, contamination was not observed in terms of contamination resistance.

  An object of the present invention is to provide a laminated film having a self-healing layer that is excellent in followability during molding and self-healing property and excellent in stain resistance.

The present invention is a laminated film having an A layer on at least one side of a base film, the A layer having (1) a (poly) caprolactone segment and (2) a urethane bond, and distilled water. the contact angle of the a layer is 95 ° or more less than 120 °, Ri contact angle 70 ° or more 87 ° less der on the a layer of diiodomethane, the a layer is derived from the following fluorine compounds a A component (hereinafter referred to as “fluorine compound A-derived component”), and the content of fluorine compound A-derived component is 0.5% by mass to 25% by mass in 100% by mass of all the components of the A layer. It is a film.
Fluorine compound A: refers to a compound represented by the following general formula (1).
B—R ¹ —R ^f —General formula (1)
(B in the above general formula represents a reactive site or a hydroxyl group, R ¹ represents an alkylene group having 1 to 3 carbon atoms and an ester structure derived therefrom, R ^f represents a fluoroalkyl group, You may have chains in the structure.)

  The laminated film of the present invention has excellent followability in warm molding, has a repair function for surface scratches (self-healing), and has excellent contamination resistance. The laminated film of the present invention is particularly effective for a resin film in which surface scratches are likely to occur.

  Hereinafter, the present invention will be described in more detail.

<Base film>
In the present invention, the resin constituting the base film may be either a thermoplastic resin or a thermosetting resin, may be a homo resin, or may be a copolymer or a blend of two or more. More preferably, the resin constituting the base film is a thermoplastic resin because of good moldability.

  Examples of thermoplastic resins include polyolefin resins such as polyethylene, polypropylene, polystyrene, and polymethylpentene, alicyclic polyolefin resins, polyamide resins such as nylon 6 and nylon 66, aramid resins, polyester resins, polycarbonate resins, and polyarylate resins. Fluorine resins such as polyacetal resin, polyphenylene sulfide resin, tetrafluoroethylene resin, trifluoroethylene resin, trifluorochloroethylene resin, tetrafluoroethylene-6 fluoropropylene copolymer, vinylidene fluoride resin, acrylic Resins, methacrylic resins, polyacetal resins, polyglycolic acid resins, polylactic acid resins, and the like can be used. The thermoplastic resin is preferably a resin having sufficient stretchability and followability. In particular, the thermoplastic resin is more preferably a polyester resin from the viewpoint of strength, heat resistance, and transparency.

  The polyester resin in the present invention is a general term for polymers having an ester bond as a main bond chain of the main chain, and is obtained by polycondensation of an acid component and its ester and a diol component. Specific examples include polyethylene terephthalate, polypropylene terephthalate, polyethylene-2,6-naphthalate, polybutylene terephthalate, and the like. These may be copolymerized with other dicarboxylic acids and their esters or diol components as acid components or diol components. Among these, polyethylene terephthalate and polyethylene-2,6-naphthalate are particularly preferable in terms of transparency, dimensional stability, heat resistance and the like.

  In addition, various additives such as an antioxidant, an antistatic agent, a crystal nucleating agent, an inorganic particle, an organic particle, a thinning agent, a heat stabilizer, a lubricant, an infrared absorber, an ultraviolet absorber, A dopant for adjusting the refractive index may be added.

  The base film may be either a single layer base film or a laminated base film.

<Polyester base film>
In this invention, when resin which comprises a base film contains 50 mass% or more and 100 mass% or less of polyester resins in 100 mass% of all the components of a base film, a base film is called polyester base film.

  In the present invention, the polyester resin constituting the polyester base film has an intrinsic viscosity of the polyester to be used (measured in o-chlorophenol at 25 ° C. according to JIS K7367 (2000)) of 0.4 to 1.2 dl / g. 0.5 to 0.8 dl / g is particularly preferable.

  The polyester base film can be any of an unstretched (non-oriented) film, a uniaxially stretched (uniaxially oriented) film, and a biaxially stretched (biaxially oriented) film, but is biaxially stretched with excellent dimensional stability and heat resistance. It is preferable to use a film. The biaxially stretched film is preferably highly crystallized. In the present invention, the biaxial orientation refers to a material that exhibits a biaxial orientation pattern by wide-angle X-ray diffraction.

  The polyester base film may be a polyester film having fine cavities inside.

  The polyester base film may have a single layer structure or a laminated structure.

  When the polyester base film has a laminated structure, different polyester resins, preferably a layer (C layer) containing 50% by mass to 100% by mass of polyester resin C and 50% by mass to 100% by mass of polyester resin D are included. The layer (D layer) to include is laminated | stacked. In the present invention, when the polyester base film has a laminated structure, the different polyester resin means a polyester resin having a different molecular structure or a case where some components of the copolymer polyester resin are different.

  When the polyester base film has a laminated structure, more preferably, a layer (C layer) containing 50% by mass or more and 100% by mass or less of polyester resin C and 50% by mass or more and 100% by mass of polyester resin D different from polyester resin C are used. % Layer (D layer) is laminated. Even more preferably, a layer (C layer) containing 50% by mass or more and 100% by mass or less of polyester resin C and a layer (D layer) containing 50% by mass or more and 100% by mass or less of polyester resin D different from polyester resin C. Alternately, it has 50 or more layers including the C layer and the D layer. The number of stacked layers is more preferably 200 layers or more. The upper limit of the number of layers is preferably 1500 layers or less in consideration of a decrease in wavelength selectivity accompanying a decrease in stacking accuracy due to an increase in the size of the device or an increase in the number of layers. In the present invention, a polyester base film having a multilayer laminated structure is preferable because it has an interference color or further a metal color.

  The polyester resin C is preferably polyethylene terephthalate or polyethylene naphthalate, and the polyester resin D is preferably a polyester containing spiroglycol. The polyester containing spiroglycol is a copolyester copolymerized with spiroglycol (polyester whose glycol component is partly spiroglycol), or a homopolyester (a homopolyester whose glycol component is all spiroglycol), or those Refers to blended polyester. Polyesters containing spiroglycol are preferred because they have a small glass transition temperature difference from polyethylene terephthalate or polyethylene naphthalate, and are therefore difficult to be overstretched during molding and are difficult to delaminate.

  More preferably, the polyester resin C is polyethylene terephthalate or polyethylene naphthalate, and the polyester resin D is a polyester containing spiroglycol and cyclohexanedicarboxylic acid. The polyester in which the polyester resin D contains spiroglycol and cyclohexanedicarboxylic acid is a polyester copolymerized with spiroglycol and cyclohexanedicarboxylic acid (or an ester derivative of cyclohexanedicarboxylic acid), or a homopolyester (the glycol component is all spiroglycol, A homopolyester in which all carboxylic acid components are cyclohexanedicarboxylic acid) or a polyester blended with this. When the polyester resin D is a polyester containing spiroglycol and cyclohexanedicarboxylic acid, a difference in in-plane refractive index from polyethylene terephthalate or polyethylene naphthalate is increased, so that high reflectance is easily obtained. Moreover, since the glass transition temperature difference with polyethylene terephthalate or polyethylene naphthalate is small, it is difficult to be over-stretched during molding, and delamination is difficult.

  The polyester resin C is preferably polyethylene terephthalate or polyethylene naphthalate, and the polyester resin D is preferably a polyester containing cyclohexanedimethanol. The polyester containing cyclohexanedimethanol refers to a copolyester obtained by copolymerizing cyclohexanedimethanol, or a homopolyester (a homopolyester in which all glycol components are cyclohexanedimethanol), or a polyester obtained by blending them. Polyesters containing cyclohexanedimethanol are preferred because they have a small glass transition temperature difference from polyethylene terephthalate or polyethylene naphthalate, and are therefore less likely to be overstretched during molding and are also difficult to delaminate.

  In the present invention, more preferably, the polyester resin D is an ethylene terephthalate polycondensate having a copolymerization amount of cyclohexanedimethanol of 15 mol% or more and 60 mol% or less. When the polyester resin D is an ethylene terephthalate polycondensate having a copolymerization amount of cyclohexanedimethanol of 15 mol% or more and 60 mol% or less, a change in optical characteristics due to heating or aging is particularly small while having high reflection performance, Peeling does not easily occur between layers. The ethylene terephthalate polycondensate having a copolymerization amount of cyclohexanedimethanol of 15 mol% or more and 60 mol% or less shows very strong compatibility with polyethylene terephthalate. In addition, the cyclohexanedimethanol group has a cis or trans isomer as a geometric isomer, and a chair type or a boat type as a conformational isomer. The optical characteristics change little due to thermal history, and it is difficult to shake during film formation.

  The in-plane average refractive index of the C layer is preferably higher than the in-plane average refractive index of the D layer. The difference between the in-plane average refractive index of the C layer and the in-plane average refractive index of the D layer is preferably 0.01 or more, and the thickness of one layer is preferably 0.03 μm or more and 0.5 μm or less. More preferably, the difference between the in-plane average refractive index of the C layer and the in-plane average refractive index of the D layer is 0.05 or more, and more preferably 0.1 or more. When the difference between the in-plane average refractive index of the C layer and the in-plane average refractive index of the D layer is 0.01 or more, the film exhibits excellent metal toning due to interference reflection. Further, when the difference between the in-plane average refractive index and the thickness direction refractive index of the C layer is 0.01 or more, and the difference between the in-plane average refractive index and the thickness direction refractive index of the D layer is 0.01 or less, the incident angle Even if becomes large, the reflectance in the reflection band does not decrease, which is more preferable.

  In this invention, it is preferable that the glass transition temperature difference of the polyester resin C and the polyester resin D is 20 degrees C or less. When the glass transition temperature difference between the polyester resin C and the polyester resin D is 20 ° C. or less, the thickness when the polyester base film in which the C layer and the D layer are laminated is formed becomes uniform, and the base film is used. Even when the laminated film is molded, cracks and peeling do not occur.

<Laminated film having A layer>
Hereinafter, a laminated film having an A layer on at least one side of the base film will be described.

  The laminated film of the present invention is a laminated film having an A layer on at least one side of the base film, and the A layer has (1) a (poly) caprolactone segment and (2) a urethane bond, It is a laminated film in which the contact angle of distilled water on the A layer is 95 ° or more and less than 120 °, and the contact angle of diiodomethane on the A layer is 70 ° or more and less than 87 °.

  The laminated film of the present invention has an effect excellent in self-healing property and stain resistance by having the A layer on at least one side of the base film.

  The A layer can be provided on both sides of the base film, but it depends on the use, but it is preferable that the A layer exists only on one side of the base film in consideration of cost. In many applications, the A layer exists only on one side of the base film, and the laminated film has sufficient self-healing property and stain resistance.

  Hereinafter, the components contained in the A layer will be described.

<(Poly) caprolactone segment>
In the present invention, the A layer has (1) (poly) caprolactone segments. By having the (poly) caprolactone segment in the A layer, the elastic recovery property (self-healing property) can be imparted to the A layer.

  In the present invention, the (poly) caprolactone segment refers to a segment represented by the following chemical formula 1.

  By forming the A layer using a composition containing a resin containing a (poly) caprolactone segment, the A layer can have a (poly) caprolactone segment. The resin containing a (poly) caprolactone segment preferably has at least one hydroxyl group (hydroxyl group). The hydroxyl group is preferably at the end of the resin containing the (poly) caprolactone segment.

  When the A layer has a component having a (poly) caprolactone segment, the A layer can have self-healing properties. That is, even if the surface of the A layer is scratched, the scratch can be extinguished (self-healed) in a short time of several seconds.

  As the resin containing a (poly) caprolactone segment, (poly) caprolactone having 2 to 3 functional hydroxyl groups is particularly preferable. Specifically, (poly) caprolactone diol,

(Poly) caprolactone triol,

Lactone modified hydroxyethyl (meth) acrylate

Radical polymerizable caprolactone such as can be used.

  In the present invention, the resin containing the (poly) caprolactone segment may contain (or copolymerize) other segments and monomers in addition to the (poly) caprolactone segment. For example, a polydimethylsiloxane segment or a polysiloxane segment may be contained (or copolymerized).

  In the present invention, the weight average molecular weight of the (poly) caprolactone segment in the resin containing the (poly) caprolactone segment is preferably 500 to 2500, and more preferably 1000 to 1500. When the weight average molecular weight of the (poly) caprolactone segment is 500 to 2500, the self-healing effect is further exhibited, and the scratch resistance is further improved.

  Regardless of whether the (poly) caprolactone segment is copolymerized or added separately, in the 100% by mass of the total components of the composition used to form the A layer, the (poly) caprolactone segment When the amount is 5 to 70% by mass, it is preferable in terms of self-healing property and stain resistance. Here, 100% by mass of all the components of the composition does not include a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

<Urethane bond>
In the present invention, the A layer has (2) a urethane bond.

  When the composition used for forming the A layer contains a urethane-modified resin, the A layer can have a urethane bond. Further, when forming the A layer, the A layer can also have a urethane bond by reacting an isocyanate group and a hydroxyl group to form a urethane bond.

  In this invention, Preferably, A layer has a urethane bond by making an isocyanate group and a hydroxyl group react, and producing | generating a urethane bond. By reacting an isocyanate group and a hydroxyl group to form a urethane bond, the toughness of the A layer can be improved and the elastic recovery property (self-healing property) can be improved.

  In addition, when a resin containing a polysiloxane segment or a resin containing a polydimethylsiloxane segment has a hydroxyl group, it is possible to generate a urethane bond between the resin and the compound having an isocyanate group by heat or the like. is there. When layer A is formed using a compound containing an isocyanate group and a resin containing a polysiloxane segment having a hydroxyl group or a resin containing a polydimethylsiloxane segment having a hydroxyl group, the toughness and elastic recovery of the A layer (self-healing) Property) can be further improved.

  In the present invention, the compound containing an isocyanate group refers to a resin containing an isocyanate group, and a monomer or oligomer containing an isocyanate group. Examples of the compound containing an isocyanate group include methylene bis-4-cyclohexyl isocyanate, trimethylolpropane adduct of tolylene diisocyanate, trimethylolpropane adduct of hexamethylene diisocyanate, trimethylolpropane adduct of isophorone diisocyanate, and tolylene diisocyanate. Polyisocyanates such as isocyanurate bodies, isocyanurate bodies of hexamethylene diisocyanate, burette bodies of hexamethylene isocyanate, and block bodies of the above isocyanates can be mentioned.

  Of these isocyanate group-containing compounds, aliphatic isocyanates are preferred because of their high self-healing properties compared to alicyclic and aromatic isocyanates. The compound containing an isocyanate group is more preferably hexamethylene diisocyanate. The isocyanate group-containing compound is particularly preferably an isocyanate having an isocyanurate ring from the viewpoint of heat resistance, and most preferably an isocyanurate of hexamethylene diisocyanate. An isocyanate having an isocyanurate ring forms a layer A having both self-healing properties and heat resistance.

  The A layer of the present invention is preferably formed by a heat reaction that generates a urethane bond with an isocyanate group and a hydroxyl group. If the isocyanate functional group of the compound containing an isocyanate group is 2 or more, it is preferable that the compound is more connected to the compound having a hydroxyl group to improve physical properties.

  In this invention, in order to form A layer, 11 mass% or more and 40 mass% or less of the compound containing an isocyanate group are included in 100 mass% of all the components of the composition used in order to form A layer. preferable. However, 100% by mass of all the components of the composition used for forming the A layer does not include a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

  In the composition used to form the A layer, melamine crosslinking agents such as alkoxymethylol melamine, acid anhydride crosslinking agents such as 3-methyl-hexahydrophthalic anhydride, amine crosslinking agents such as diethylaminopropylamine, etc. Other crosslinkers can also be included. If necessary, a crosslinking catalyst such as dibutyltin dilaurate or dibutyltin diethylhexoate may be used to promote the urethane bond formation reaction.

  In the present invention, the A layer preferably contains a resin having all of (1) (poly) caprolactone segment, (2) urethane bond, (3) polysiloxane segment and / or polydimethylsiloxane segment. The (A) layer is formed by including all of (1) (poly) caprolactone segment, (2) urethane bond, (3) polysiloxane segment and / or polydimethylsiloxane segment in one resin which is a polymer. Is preferable because it becomes a tougher layer.

  A composition containing at least three components of a polydimethylsiloxane copolymer having a hydroxyl group, (poly) caprolactone, and an isocyanate group-containing compound is applied onto a base film and reacted by heating to obtain (poly) A layer having a resin having all of caprolactone segment, polydimethylsiloxane segment and urethane bond can be obtained.

  In 100% by mass of all components constituting the A layer, the A layer is composed of (1) (poly) caprolactone segment, (2) urethane bond, (3) (poly) siloxane segment and / or (poly) dimethylsiloxane segment. It is more preferable to occupy 80 mass% or more and 100 mass% or less of resin which has this. In 100% by mass of all components constituting layer A, the resin having all of (poly) caprolactone segment, polysiloxane segment and / or polydimethylsiloxane segment and urethane bond accounts for 80% by mass or more and 100% by mass or less. , Self-healing is increased.

<Polysiloxane segment>
In the present invention, the A layer preferably has (3) a polysiloxane segment. In the present invention, the polysiloxane segment refers to a segment represented by the following chemical formula. In the following chemical formula 5, R is either OH or an alkyl group having 1 to 8 carbon atoms, and each has at least one or more in the formula.

  In order for the A layer to have a polysiloxane segment, the composition used for forming the A layer includes a resin containing the polysiloxane segment.

  In the present invention, a partial hydrolyzate of a silane compound containing a hydrolyzable silyl group, an organosilica sol or a composition obtained by adding a hydrolyzable silane compound having a radical polymer to the organosilica sol contains a polysiloxane segment. It can be used as a resin.

  Resins containing polysiloxane segments are tetraalkoxysilane, methyltrialkoxysilane, dimethyldialkoxysilane, γ-glycidoxypropyltrialkoxysilane, γ-glycidoxypropylalkyldialkoxysilane, γ-methacryloxypropyltrimethyl. A hydrolyzable silyl group on the surface of an organosilica sol dispersed in a complete or partial hydrolyzate of a silane compound having a hydrolyzable silyl group such as alkoxysilane or γ-methacryloxypropylalkyldialkoxysilane or an organic solvent. The thing etc. which added the hydrolysis silane compound of this can be illustrated.

  In the present invention, the resin containing a polysiloxane segment may contain (copolymerize) other segments in addition to the polysiloxane segment. For example, a monomer component having a (poly) caprolactone segment and a polydimethylsiloxane segment may be contained (copolymerized).

  In the present invention, it is preferable that a monomer having a hydroxyl group that reacts with an isocyanate group is copolymerized as a resin containing a polysiloxane segment. When a resin having a hydroxyl group that reacts with an isocyanate group is copolymerized with a resin containing a polysiloxane segment, the toughness of the A layer is improved.

  When the resin containing a polysiloxane segment is a copolymer having a hydroxyl group, a layer A is formed using a composition containing a resin containing a hydroxyl group-containing polysiloxane segment (copolymer) and a compound containing an isocyanate group. When A is formed, an A layer having a polysiloxane segment and a urethane bond can be efficiently formed.

  Regardless of whether the polysiloxane segment is copolymerized or added separately, the polysiloxane segment is 1 to 20% by mass in 100% by mass of the total component of the composition used to form the A layer. % Is preferable in terms of self-healing property, stain resistance, weather resistance, and heat resistance. 100% by mass of the total components of the composition does not include a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

<Polydimethylsiloxane segment>
In the present invention, the A layer preferably has (3) a polydimethylsiloxane segment.

  In the present invention, the polydimethylsiloxane segment refers to a segment represented by the following formula.

  When the A layer has a polydimethylsiloxane segment, the polydimethylsiloxane segment is present on the surface of the A layer. When the polydimethylsiloxane segment is present on the surface of the A layer, the lubricity of the surface of the A layer is improved and the frictional resistance can be reduced. As a result, scratchability can be suppressed.

  In order for the A layer to have the polydimethylsiloxane segment, the composition used for forming the A layer can include a resin containing the polydimethylsiloxane segment. In the present invention, as the resin containing a polydimethylsiloxane segment, it is preferable to use a copolymer obtained by copolymerizing a vinyl monomer with a polydimethylsiloxane segment.

  For the purpose of improving the toughness of the A layer, the resin containing a polydimethylsiloxane segment is preferably copolymerized with a monomer having a hydroxyl group that reacts with an isocyanate group. When the resin containing a polydimethylsiloxane segment is a copolymer having a hydroxyl group, a composition containing a resin containing a hydroxyl group-containing polydimethylsiloxane segment (copolymer) and a compound containing an isocyanate group is used. When the A layer is formed, the A layer having a polydimethylsiloxane segment and a urethane bond can be efficiently formed.

  When the resin containing the polydimethylsiloxane segment is a copolymer with a vinyl monomer, it may be a block copolymer, a graft copolymer, or a random copolymer. When the resin containing the polydimethylsiloxane segment is a copolymer with a vinyl monomer, this is referred to as a polydimethylsiloxane copolymer. Polydimethylsiloxane copolymers can be produced by the living polymerization method, polymer initiator method, polymer chain transfer method, etc., but considering the productivity, the polymer initiator method, polymer chain transfer method can be used. It is preferable to use it.

  When using the polymer initiator method, the chemical formula

It can be made to copolymerize with other vinyl monomers using the polymer azo radical polymerization initiator shown by these. In addition, a two-stage polymerization is carried out by synthesizing a prepolymer in which a peroxide group is introduced into the side chain by copolymerizing a peroxy monomer and polydimethylsiloxane having an unsaturated group at a low temperature, and then copolymerizing the prepolymer with a vinyl monomer. Can also be done.

  When using the polymer chain transfer method, for example, the following chemical formula

After adding HS—CH ₂ COOH, HS—CH ₂ CH ₂ COOH, etc. to the silicone oil shown in FIG. 4 to obtain a compound having an SH group, the silicone compound and the vinyl monomer are combined using chain transfer of the SH group. A block copolymer can be synthesized by copolymerization.

  To synthesize a polydimethylsiloxane-based graft copolymer, for example, the following chemical formula

A graft copolymer can be easily obtained by copolymerizing a compound shown in the following, that is, a methacrylic ester of polydimethylsiloxane and a vinyl monomer.

  Examples of vinyl monomers used in the copolymer with polydimethylsiloxane include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, octyl acrylate, cyclohexyl acrylate, tetrahydrofurfuryl acrylate, methyl methacrylate, ethyl methacrylate, n -Butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, stearyl methacrylate, lauryl methacrylate, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, styrene, α-methyl styrene, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl chloride, vinylidene chloride , Vinyl fluoride, vinylidene fluoride, glycidyl acrylate Glycidyl methacrylate, allyl glycidyl ether, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, maleic anhydride, acrylamide, methacrylamide, N-methylolacrylamide, N, N-dimethylacrylamide, N, N-dimethylaminoethyl Examples thereof include methacrylate, N, N-diethylaminoethyl methacrylate, diaceton acrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, and allyl alcohol.

  Polydimethylsiloxane copolymers include aromatic hydrocarbon solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate and butyl acetate, ethanol, isopropyl alcohol, etc. It is preferable that the alcoholic solvent is produced by a solution polymerization method alone or in a mixed solvent.

  If necessary, a polymerization initiator such as benzoyl peroxide or azobisisobutylnitrile is used in combination. The polymerization reaction is preferably performed at 50 to 150 ° C. for 3 to 12 hours.

  The amount of the polydimethylsiloxane segment in the polydimethylsiloxane copolymer in the present invention is 1 to 30 in 100% by mass of all components of the polydimethylsiloxane copolymer in terms of the lubricity and stain resistance of the A layer. It is preferable that it is mass%. The weight average molecular weight of the polydimethylsiloxane segment is preferably 1000-30000.

  Whether the polydimethylsiloxane segment is copolymerized or added separately, the dimethylsiloxane segment is 1 to 20 in 100% by mass of the total components of the composition used to form the A layer. The mass% is preferable in terms of self-healing property, contamination resistance, weather resistance, and heat resistance. 100% by mass of the total components of the composition does not include a solvent that does not participate in the reaction. The monomer component involved in the reaction is included.

  In the present invention, when a resin containing a polydimethylsiloxane segment is used as the composition used to form the A layer, other segments are contained (copolymerized) in addition to the polydimethylsiloxane segment. Also good. For example, a (poly) caprolactone segment or a polysiloxane segment may be contained (copolymerized).

  The composition used to form the A layer includes a copolymer of (poly) caprolactone segment and polydimethylsiloxane segment, a copolymer of (poly) caprolactone segment and polysiloxane segment, (poly) caprolactone segment and poly A copolymer of a dimethylsiloxane segment and a polysiloxane segment can be used. The A layer obtained using such a composition can have a (poly) caprolactone segment and a polydimethylsiloxane segment and / or a polysiloxane segment.

  The reaction of the polydimethylsiloxane-based copolymer, (poly) caprolactone, and polysiloxane in the composition used to form the layer A having (poly) caprolactone segment, polysiloxane segment, and polydimethylsiloxane segment is When synthesizing the dimethylsiloxane-based copolymer, a (poly) caprolactone segment and a polysiloxane segment can be appropriately added and copolymerized.

<Fluorine compound A>
In this invention, it is preferable that A layer contains the component (henceforth a fluorine compound A origin component) derived from the following fluorine compounds A. By including the component derived from the fluorine compound A, the A layer can impart stain resistance to the A layer.

In the present invention, the fluorinated compound A refers to a compound represented by the following general formula (1).
B—R ¹ —R ^f —General formula (1)
(B in the above general formula represents a reactive site or a hydroxyl group, R ¹ represents an alkylene group having 1 to 3 carbon atoms and an ester structure derived therefrom, R ^f represents a fluoroalkyl group, You may have chains in the structure.)
The reactive site of B means a site having a functional group that chemically reacts with radicals generated by receiving energy such as light or heat, or a hydroxyl group. Specific examples of the site having a functional group that chemically reacts with radicals generated by receiving energy such as light or heat include a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. In the present invention, since the A layer has a urethane bond, B may be a hydroxyl group.

  Further, the fluoroalkyl group is a substituent in which all hydrogens of the alkyl group are replaced with fluorine, and is a substituent composed of only a fluorine atom and a carbon atom.

  Examples of the fluorine compound A include 2- (perfluorobutyl) ethanol, 2- (perfluorohexyl) ethanol, 2- (perfluorobutyl) ethyl acrylate, 2- (perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl acrylate, Fluorobutyl) ethyl methacrylate, 2- (perfluorohexyl) ethyl methacrylate, perfluorohexylethylene, 3- (perfluorohexyl) propylene and the like can be mentioned.

  Among these fluorine compounds A, when B is an acryloyl group, contamination resistance is particularly high and preferable. The fluorine compound A in which B contains an acryloyl group is more preferably 2- (perfluorohexyl) ethyl acrylate.

  When the composition used to form the A layer contains the fluorine compound A, the A layer obtained using the composition can contain a component derived from the fluorine compound A.

  Moreover, it is preferable to contain 0.5 mass% or more and 25 mass% or less of fluorine compound A origin components in 100 mass% of all the components of the composition used in order to form A layer. By making the composition used for forming the A layer in this way, the component derived from the fluorine compound A is 0.5% by mass or more and 25% by mass or less in 100% by mass of all the components of the A layer of the obtained laminated film. Thus, the self-healing property and contamination resistance of the A layer can be made particularly excellent. That is, while maintaining excellent self-healing property, even if dioctyl phthalate derived from a PVC sheet or cosmetics adheres to the surface of the A layer, it can be removed cleanly by wiping.

In the present invention, when the fluorine compound A is contained in the composition used for forming the A layer, in addition to the fluorine compound A, other fluorine compounds may be contained. Examples of such compounds include hexafluoropropylene, hexafluoropropylene oxide, perfluoro (propyl vinyl ether), perfluorohexyl iodide, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, and the like. May be.
<Other additives>
The composition used for forming the A layer preferably contains an initiator, a curing agent, and a catalyst. An initiator and a catalyst are used to accelerate the curing of the fluorine compound A. As the initiator, those capable of initiating or accelerating polymerization, condensation or crosslinking reaction of the coating composition by anion, cation, radical reaction or the like are preferable.

  Various initiators, curing agents and catalysts can be used. In addition, the initiator, the curing agent, and the catalyst may be used alone, or a plurality of initiators, curing agents, and catalysts may be used at the same time. Furthermore, you may use together an acidic catalyst, a thermal-polymerization initiator, and a photoinitiator. Examples of acidic catalysts include aqueous hydrochloric acid, formic acid, acetic acid and the like. Examples of the thermal polymerization initiator include peroxides and azo compounds. Examples of the photopolymerization initiator include alkylphenone compounds, sulfur-containing compounds, acylphosphine oxide compounds, amine compounds, and the like. As the photopolymerization initiator, an alkylphenone compound is preferable from the viewpoint of curability. Specific examples of the alkylphenone type compounds include 1-hydroxy-cyclohexyl-phenyl-ketone, 2.2-dimethoxy-1.2-diphenylethane-1-one, 2-methyl-1- (4-methylthiophenyl)- 2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-phenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) methyl]- 1- (4-phenyl) -1-butane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butane, 2- (dimethylamino) -2-[(4-methylphenyl) ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butane, 1-cyclohexyl-phenyl ketone, 2-methyl-1-phenylpropan-1-one, 1- [4- ( - ethoxy) - phenyl] -2-hydroxy-2-methyl-1-like.

  In addition, as for the content rate of the initiator and hardening | curing agent in the composition used in order to form A layer, 0.001 mass part to 30 mass parts is preferable with respect to 100 mass parts of fluorine compounds A. More preferably, it is 0.05 mass part to 20 mass parts, More preferably, it is 0.1 mass part to 10 mass parts.

<Other components of layer A>
The A layer of the present invention may contain other components such as an acrylic segment, a polyolefin segment, and a polyester segment.

  The polyolefin segment is a polymer composed of repeating units derived from an olefin having 2 to 20 carbon atoms having a structure equivalent to that of a polyolefin resin.

  The acrylic segment is a polymer containing an acrylic unit as a constituent component, and preferably contains 50 mol% or more of the acrylic unit. Preferable examples include methyl methacrylate unit, acrylmethyl unit, acrylethyl unit and acrylbutyl unit. If the A layer has an acrylic segment, the A layer can be made excellent in stain resistance and toughness.

  As the diol component of the polyester segment, in addition to butanediol and / or hexanediol, ethylene glycol, 1,3-propanediol, neopentyl glycol, 2-methyl 1,3-propanediol, 1,4-cyclohexanedimethanol, Polytetramethylene glycol, polyethylene glycol, polypropylene glycol, dimer diol, and hydrogenated dimer diol can be used. As the acid component of the polyester segment, terephthalic acid, naphthalenedicarboxylic acid, isophthalic acid, sebacic acid, adipic acid, azelaic acid, succinic acid, hexahydroterephthalic acid, and the like can be used, and a plurality of these components are included. May be.

  For example, a heat-resistant agent, an ultraviolet absorber, a light stabilizer, organic and inorganic particles, a pigment, a dye, a release agent, and an antistatic agent can be added to the A layer.

<Glass transition temperature (Tg) of layer A>
In the laminated film of the present invention, the glass transition temperature (Tg) of the A layer is preferably −30 ° C. or higher and 15 ° C. or lower. The glass transition temperature (Tg) of the A layer is more preferably 0 ° C. or higher and 15 ° C. or lower.

  When the glass transition temperature of the A layer is −30 ° C. or more and 15 ° C. or less, the self-healing rate is greatly improved, and a laminated film that maintains the self-healing property even in a low temperature region is obtained. When the glass transition temperature of the A layer exceeds 15 ° C., the self-healing property at an ambient temperature of 10 ° C. or less is extremely slow, and when the glass transition temperature of the A layer is less than −30 ° C., the slip property is lowered. This causes problems such as winding failure on the roll, blocking, and molding defects. When the glass transition temperature of the A layer is 0 ° C. or higher and 15 ° C. or lower, the self-healing property at the atmospheric temperature of 5 ° C. is good and the contamination resistance is good.

  In order to set the glass transition temperature of the A layer to −30 ° C. or more and 15 ° C. or less, the compound containing an isocyanate group is contained in an amount of 11 to 40% by mass in 100% by mass of all the components used for forming the A layer. % Is preferable.

  As another method for setting the glass transition temperature of the A layer to −30 ° C. or more and 15 ° C. or less, the A layer preferably has a low glass transition temperature component. In particular, the A layer preferably has an acrylic segment having a low glass transition temperature component. The acrylic segment of the low glass transition temperature component is a segment composed of a polymer of monomers such as n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, and isobutyl methacrylate. It is preferable because the glass transition temperature of the A layer can be controlled to -30 ° C. or higher and 15 ° C. or lower by changing the content of the acrylic segment of the low glass transition temperature component in the A layer.

<Scratch recovery time at 10 ° C. of layer A>
The laminated film of the present invention preferably has a wound recovery time of 25 seconds or less at a temperature of 10 ° C. of the A layer. More preferably, the scratch recovery time at a temperature of 10 ° C. of the A layer is 10 seconds or less. When the recovery time is 25 seconds or less, the self-healing speed is greatly improved. A recovery time of 10 seconds or less is preferable because even if the molding magnification is increased, the decrease in self-healing property is small. The laminated film of the present invention has a different recovery time depending on the temperature. It has been found that the lower the temperature, the longer the recovery time and the higher the temperature, the shorter the recovery time. In addition, the laminated film of the present invention has a slightly different recovery time depending on the base film. It is known that the recovery time is shortened if the base film is the laminated configuration, and the recovery time is prolonged if the single-layer configuration is, but the change is 1 second or less when the temperature of the A layer is 10 ° C. The contribution to recovery time is negligible.

In order to make the recovery time of scratches at a temperature of 10 ° C. of the A layer 25 seconds or less, it is preferable to lower the glass transition temperature of the A layer, and the recovery time of scratches at the temperature of the A layer of 10 ° C. is 25 seconds or less. Therefore, the glass transition temperature of the A layer is preferably −30 ° C. or higher and 15 ° C. or lower.
<Distribution of fluorine atoms>
In the laminated film of the present invention, when the total number of fluorine atoms, carbon atoms, nitrogen atoms, oxygen atoms, and silicon atoms detected by XPS is 100%, the number of fluorine atoms is 0. It is preferably 4% or more and 50% or less, and more preferably 10% or more and 50% or less. Contamination resistance can be made particularly excellent by setting the number of fluorine atoms to 0.4% or more and 50% or less on the surface of the A layer side. Regarding the surface of the A layer side, the method of adjusting the number of fluorine atoms to 0.4% or more and 50% or less is that 0.5% by mass or more and 25% by mass of the fluorine compound A-derived component in 100% by mass of all components of the A layer % Or less is preferable.

  When the total thickness of the A layer is 100%, the laminated film of the present invention has a TOF-SIMS in the range of 1% to 100% in thickness from the A layer side surface of the laminated film toward the base film direction. The maximum value of the fluorine atom detection intensity by TOF-SIMS in the range from 0% to less than 1% in thickness from the surface of the laminated film A layer side to the base film direction. When the value is b, a / b is preferably 0% or more and 60% or less, more preferably 5% or more and 25% or less. By setting it as such a structure, self-healing property and contamination resistance can be made compatible.

  Here, a means one point indicating the maximum value among the detected intensities of a plurality of fluorine atoms detected in this range. The same applies to b.

  a / b is more preferably 5% or more and 20% or less.

In addition, the said fluorine compound A (component derived from a fluorine compound) has the characteristics which gather on the surface and harden | cure. Therefore, in order to obtain a laminated film having a configuration where a / b is 0% or more and 60% or less, it is preferable that the composition used for forming the A layer contains the fluorine compound A.
<Number of layers A>
In the laminated film of the present invention, it is preferable that the layer on at least one side of the base film is composed of only one A layer.

  The layer A of the laminated film of the present invention preferably contains a component derived from the fluorine compound A. For example, the layer A was obtained through the laminating step, the heating step, and the aging step described below without containing the component derived from the fluorine compound A. ) When a layer containing a fluorine compound A-derived component is further laminated on the A layer having (poly) caprolactone segment and (2) urethane bond, the surface properties greatly depend on the fluorine compound A-derived component, Although contamination resistance is obtained, self-healing property cannot be obtained. For this reason, the A layer is a layer having a fluorine compound A-derived component and a (poly) caprolactone segment, etc., rather than two or more layers in which a layer made of the fluorine compound A is laminated on a layer having a (poly) caprolactone segment or the like. An embodiment consisting of only one layer is preferred.

  That is, it is preferable that the A layer itself having (1) (poly) caprolactone segment and (2) urethane bond contains a fluorine compound A-derived component.

  In the present invention, the term “only one layer” means a layer having no interface in which the difference in luminance is 5% or more. Details will be described later.

  In the present invention, since the number of layers is preferably one, when producing the laminated film of the present invention, only the composition containing the fluorine compound A is used as a composition for forming the A layer. It is preferable to apply and cure. When the composition containing the fluorine compound A is applied to the base film and cured, the fluorine compound A moves to the surface of the layer A, so it is composed of one layer, and there is a concentration distribution among the contained components in the layer. The laminated film of the present invention can be obtained. That is, the laminated film of the present invention is preferably a laminated film obtained by curing the composition used for forming the A layer containing the fluorine compound A, after coating the substrate film only once. .

<Performance of layer A>
In the laminated film of the present invention, it is important that the contact angle on the A layer of distilled water is 95 ° or more and less than 120 °, and the contact angle on the A layer of diiodomethane is 70 ° or more and less than 87 °. .

  The contact angle on the A layer of distilled water is more preferably 105 ° or more and less than 120 °, and still more preferably 95 ° or more and less than 120 °. Further, the contact angle of the diiodomethane on the A layer is more preferably 75 ° or more and less than 87 °, and further preferably 80 ° or more and less than 87 °.

  If the contact angle on the A layer of distilled water is 95 ° or more and less than 120 °, and the contact angle on the A layer of diiodomethane is 70 ° or more and less than 87 °, the stain resistance will be good. Contamination resistance refers to resistance to dioctyl phthalate and the like derived from creams, oil-based magic, and vinyl chloride sheets having a skin-beautifying effect and an ultraviolet blocking effect.

  In order for the contact angle on the A layer of distilled water to be 95 ° or more and less than 120 ° and the contact angle on the A layer of diiodomethane to be 70 ° or more and less than 87 °, In addition, it is preferable that the component derived from the fluorine compound A is contained in an amount of 0.5% by mass or more and 25% by mass or less.

  In order to obtain the laminated film of the present invention, the A layer is laminated to form an A1 layer having (1) (poly) caprolactone segments and (2) urethane bonds on the base film, and then the A1 layer It is also possible to form an A2 layer having a contact angle with distilled water of 95 ° or more and less than 120 ° and a contact angle with diiodomethane of 70 ° or more and less than 87 °. However, in the case of such a configuration, since it does not have sufficient self-healing property, it is inferior in function, and since the two layers are configured separately, it is not desirable in terms of cost. On the other hand, if it is the laminated film of this invention obtained by making the composition used in order to form A layer containing the fluorine compound A apply | coat only once on a base film, and making it harden | cure, it is A layer The total number is one layer, and a laminated film excellent in function and cost can be obtained.

  In addition, in order to control the contact angle of the diiodomethane on the A layer to 80 ° or more and less than 87 °, it is more important to manufacture under special conditions. That is, in order to control the contact angle of the diiodomethane on the A layer to 80 ° or more and less than 87 °, it is important to collect fluorine atoms on the surface. In order to make the contact angle on the A layer of diiodomethane 70 ° or more and less than 87 °, it is possible to simply form the A layer using a composition containing the fluorine compound A, but the contact angle is 80 °. In order to control the angle to be less than 87 °, it is required to further collect fluorine atoms on the surface.

  In order to collect the fluorine compound A on the surface more efficiently and cure it in the state of collecting on the surface, that is, to collect the fluorine compound A-derived component on the surface of the A layer, the fluorine compound A in the coating liquid moves to the surface of the A layer. It is effective to reduce the movement resistance until it is done. For that purpose, it is effective to suppress the hardening of the material forming the A layer other than the fluorine compound A. For example, it is preferable to mix and use a high boiling point solvent (for example, cyclohexanone or butyl acetate) together with a low boiling point solvent (for example, methyl ethyl ketone or ethyl acetate) in the composition used for forming the A layer. Here, the low boiling point solvent is preferably a solvent having a boiling point of 80 ° C. or lower, more preferably 75 ° C. or higher and 80 ° C. or lower. On the other hand, the high boiling point solvent is preferably a solvent having a boiling point of 125 ° C. or higher, more preferably 125 ° C. or higher and 160 ° C. or lower. Moreover, as for the mass ratio of these solvents, it is preferable that a high boiling point solvent: low boiling point solvent is 1-50: 99-50. Furthermore, in the energy ray irradiation process described later, it is preferable that the oxygen concentration in the process be 2% by volume or less by performing the process in a nitrogen atmosphere because the curing of the fluorine compound A is not inhibited by oxygen. Further, when forming the A layer, the fluorine compound A is preferably cured by irradiation with energy rays, and the other materials for forming the A layer are preferably cured by heat. That is, the step of applying the composition used to form the A layer containing the fluorine compound A only once on the base film, the energy ray irradiation step, the heating step described later, and the aging step described later It is preferable to form A layer by carrying out in order. By performing these operations, the contact angle of diiodomethane on the A layer can be set to 80 ° or more and less than 87 °, which is preferable.

  In the laminated film of the present invention, in order to obtain a laminated film having good self-healing properties and cosmetic resistance, the thickness of the A layer is preferably 15 to 30 μm. By setting the thickness of the A layer to 15 to 30 μm, a laminated film having a self-healing effect and having good cosmetic resistance can be obtained.

  When the laminated film of the present invention is molded, since the thickness of the A layer is reduced by molding, it is effective to increase the thickness of the A layer in accordance with the molding magnification. The preferred thickness of the A layer in molding at a molding magnification of 1.1 times is 16.5 to 33 μm, and the preferred thickness of the A layer in molding at a molding magnification of 1.6 times is 24 to 48 μm.

  The average breaking elongation at 80 ° C. and 150 ° C. of the layer A of the laminated film of the present invention is preferably 65% or more and less than 100%, more preferably 70% or more and less than 100%. When the average breaking elongation at 80 ° C. and 150 ° C. is 65% or more, sufficient elongation can be maintained, and when it is less than 100%, the followability with the base film is good.

<Method for forming layer A>
The layer A of the laminated film of the present invention can be produced, for example, through the following steps in that order. In order to make the average breaking elongation at 80 ° C. and 150 ° C. of the A layer 65% or more and less than 100%, it is particularly preferable to go through an aging step after the laminating step, the heating step, and the energy ray irradiation step.

Laminating step (1) (poly) caprolactone segment, (3) polysiloxane segment and / or polydimethylsiloxane segment, (2) urethane bond, fluorine compound A layer (A layer) on at least one side of the base film Are laminated. Lamination of the A layer to the base film includes, for example, a method of applying a composition used to form the A layer and, if necessary, a coating liquid containing a solvent to at least one side of the base film. Can do. As the coating method, a known coating method such as a gravure coating method, a micro gravure coating method, a die coating method, a reverse coating method, a knife coating method, or a bar coating method can be applied.

Heating step By heating, the solvent in the layer volatilizes, and the crosslinking reaction between the isocyanate group in the composition used for forming the A layer and other segments can be promoted. In the present invention, after the heating step, the remaining amount of isocyanate groups in the A layer before the aging step is preferably 10% or less, more preferably 5% or less, based on the amount of isocyanate groups before the heating step. More preferably, it is substantially 0%. Substantially 0% means that an isocyanate group is not detected even when infrared spectrophotometric analysis is performed. When a large amount of isocyanate groups remain in the A layer, in the subsequent aging process, the isocyanate group in the A layer reacts with moisture in the air to form a urea bond, and the A layer after the aging process becomes hard. This causes the average fracture elongation of the A layer to decrease. Therefore, it is desirable that the isocyanate group reaction is allowed to proceed as much as possible (more preferably) before the aging step. When the reaction is insufficient, tackiness remains in the A layer, and when it is wound into a roll, blocking with the opposite surface occurs, and it may be difficult to peel off after aging.

  The heating temperature in the heating step is preferably 60 ° C. or higher, more preferably 80 ° C. or higher. Considering the generation of wrinkles due to heat shrinkage of the base film, the heating temperature is preferably 180 ° C. or less, and considering the volatilization of the fluorine compound A by heating, it is preferably 160 ° C. or less, more preferably It is preferable that it is 100 degrees C or less. When the heating temperature is 60 ° C. or higher, the solvent is sufficiently volatilized.

  The heating time is 1 minute or longer, preferably 2 minutes or longer, more preferably 3 minutes or longer. From the viewpoint of maintaining productivity, dimensional stability of the base film, and transparency, the heating time is desirably 5 minutes or less.

  In this invention, it is preferable that heating temperature is 60 degreeC or more and 160 degrees C or less, and heating time is 1 minute or more and 5 minutes or less. The heating method in the heating step is preferably performed with hot air from the viewpoint of heating efficiency, and a known hot air dryer or a hot air furnace capable of continuous conveyance such as roll conveyance or floating can be applied.

Energy ray irradiation process Fluorine compound A in the composition used for forming the A layer can be cured by irradiating energy rays. Curing with energy rays is preferably electron beams (EB rays) or ultraviolet rays (UV rays) from the viewpoint of versatility. In the case of curing with ultraviolet rays, the oxygen concentration is preferably 2% by volume or less, more preferably 0% by volume because oxygen inhibition can be prevented, and therefore, under a nitrogen atmosphere (nitrogen purge). It is preferable to cure. When the oxygen concentration is as high as 18% by volume or more, the curing of the outermost surface is inhibited, the curing becomes insufficient, and the self-healing property and the stain resistance may be insufficient. Examples of the ultraviolet lamp used when irradiating ultraviolet rays include a discharge lamp method, a flash method, a laser method, and an electrodeless lamp method. Case of UV cured using a high pressure mercury lamp is a discharge lamp type, illuminance of ultraviolet rays is 100 mW / cm ² or more 3000 mW / cm ² or less. Illuminance of ultraviolet is preferably 200 mW / cm ² or more 2000 mW / cm ² or less, more preferably 300 mW / cm ² or more 1500 mW / cm ² or less. Integrated quantity of ultraviolet light is 100 mJ / cm ² or more 3000 mJ / cm ² or less. Integrated light quantity preferably is 200 mJ / cm ² or more 2000 mJ / cm ² or less, more preferably 300 mJ / cm ² or more 1500 mJ / cm ² or less. Here, the ultraviolet illuminance is the irradiation intensity received per unit area, and varies depending on the lamp output, the emission spectrum efficiency, the diameter of the light emitting bulb, the design of the reflecting mirror, and the light source distance to the irradiated object. However, the illuminance does not change depending on the conveyance speed. Further, the UV integrated light amount is irradiation energy received per unit area, and is the total amount of photons reaching the surface. The integrated light quantity is inversely proportional to the irradiation speed passing under the light source, and is proportional to the number of irradiations and the number of lamps. When curing is performed by heat, the drying step and the curing step may be performed simultaneously.

Aging Step In the heating step, the heated laminated film is preferably subjected to an aging treatment after passing through the energy ray irradiation step. The aging temperature is preferably 20 to 60 ° C, more preferably 40 to 60 ° C. The aging time is preferably 3 days or more, more preferably 7 days or more, and still more preferably 20 days or more. Since the urethane bond is increased by the aging treatment and the average breaking elongation of the A layer can be 65% or more and less than 100%, it is preferable that the curing of the A layer is completed by the aging process. The aging treatment is preferably carried out by a single wafer or a roll in a temperature-controlled room where a predetermined temperature can be set.

  A preferred application of the laminated film of the present invention is a molding application, particularly a decorative molding application applied to a housing such as a personal computer or a mobile phone. The laminated film of the present invention can be formed into a molded body by applying a molding method such as injection molding, pressure molding, vacuum molding, thermoforming, press molding or the like. Especially, it can apply especially suitably for the use heated at 80 to 180 degreeC at the time of shaping | molding.

  Moreover, when using for a shaping | molding use, it is preferable that the shaping | molding magnification of the laminated | multilayer film of this invention is 1.1 to 1.6 times. In the molded body, a bending portion or a curved portion is particularly likely to have a high molding magnification, and if the molding magnification of the bent portion or the curved portion is 1.1 to 1.6 times, it is preferable because it can support deep drawing. .

  The laminated film of the present invention can also be suitably used as a touch panel comprising the laminated film.

[Characteristic measurement method and effect evaluation method]
The characteristic measurement method and effect evaluation method in the present invention are as follows.

(1) A layer thickness and layer thickness:
The cross sections of the laminated film and the molded film are obtained by cutting with a diamond knife of a microtome (manufactured by Nippon Microtome, RMS-50) (referred to as method A. A sample obtained by method A is referred to as sample A). After that, it is left to stand in a 1% by mass osmium tetroxide solution (4 ° C.) for 2 hours. A sample is obtained by washing three times with 100 ml of ethanol having a purity of 99.8% by mass or more for 20 minutes while shaking (referred to as method B. The sample obtained by method B is referred to as sample B). Further, another sample having the same operation is prepared using a 1% by mass ruthenium tetroxide solution (referred to as method C. The sample obtained by method C is referred to as sample C). For these samples A, B, and C, an image enlarged up to 40,000 times according to the layer thickness observed with a transmission electron microscope (H-7100FA manufactured by Hitachi, Ltd.) was obtained, and the highest contrast was obtained. The method by which samples were obtained was selected.

And the layer thickness was measured about the sample of the selected specific method. The measurement was an average value of 10 samples in the selected method. Moreover, the measurement part cut out 50mm square of the center part of a sample, and measured three places in it.
Number of layers:
The number of layers is measured by examining the luminance of the image used for measuring the layer thickness using image analysis software Image-Pro Plus manufactured by Nippon Roper. And the brightness | luminance which the layer laminated | stacked on a base film has is measured, and it is judged whether the interface from which a brightness | luminance difference becomes 5% or more can be set in the direction substantially parallel to a base film.

  That is, when the brightness of the layer laminated on the base film is measured and an interface where the brightness difference is 5% or more in a direction substantially parallel to the base film can be found, the structure is composed of two or more layers. Shall be. On the other hand, when measuring the brightness of the layer laminated on the base film, it is not possible to find an interface with a brightness difference of 5% or more in the direction substantially parallel to the base film, and it is composed of one layer. Shall be.

  In addition, in order to determine whether or not an interface with a luminance difference of 5% or more can be set in a direction substantially parallel to the base film, even if there is a portion with a luminance difference of 5% or more, If there is only one part and an interface where the difference in luminance is 5% or more cannot be set in a direction substantially parallel to the base film, the layer is composed of one layer.

  In addition, since it is difficult to observe a layer having a thickness of less than 0.01 nm, the layer having a thickness of less than 0.01 nm is ignored.

(2) Average fracture elongation of layer A at 80 ° C. and 150 ° C. The laminated film was cut into a length of 10 mm × 200 mm and held in a longitudinal direction with a chuck, and an Instron type tensile tester (Instron ultra-precision material test) Machine model 5848) was stretched at a pulling speed of 100 mm / min. A measurement atmosphere temperature was set to 80 ° C., and a sample was collected in units of elongation of 1%. Cut out the thin film cross section of the collected sample and observe the A layer at a magnification such that the thickness of the A layer to be observed is 30 mm or more on the observation screen of the transmission electron microscope, and 50% or more of the average thickness of the A layer When the crack (crack) was generated, it was determined that there was a crack (A layer was broken), and the breaking elongation (80 ° C.—first time) of the film. The same measurement was performed three times in total to obtain the breaking elongation (80 ° C.—first time), the breaking elongation (80 ° C.—the second time) and the breaking elongation (80 ° C.—the third time). The average breaking elongation of the A layer at 80 ° C. was used.

  Subsequently, the average fracture elongation of the A layer at 150 ° C. was determined in the same manner as when the measurement atmosphere temperature was 80 ° C. except that the measurement atmosphere temperature was 150 ° C.

(3) Number of fluorine atoms on the surface of layer A (X-ray photoelectron spectroscopy: XPS)
The measurement was performed with an ULVAC-PHI PHI5000 VersaProbe. The conditions are as follows.
X-ray source: mono-Al
Output: 24.2W
X-ray beam diameter: 100 μm
Extraction angle: 45 °
Pass energy: 23.50 eV
The composition ratio of each atom is determined by measuring the peak area from the high resolution spectrum and applying the transfer function modified atomic sensitivity constant, and the attached software is used for the analysis.

  Then, the number of fluorine atoms when the total number of fluorine atoms, carbon atoms, nitrogen atoms, oxygen atoms, and silicon atoms detected by XPS was set to 100% on the surface of the layer A side of the laminated film was determined (Table). In the above, it is described as “fluorine atom number ratio [%] on the surface of layer A”). When this measurement was below the detection limit (when no fluorine atom was detected), “-” was shown in the table.

(4) a / b (time-of-flight secondary ion mass spectrometry: TOF-SIMS)
Using TOF-SIMSV manufactured by ION TOF, the detection intensity of fluorine atoms by secondary ion mass spectrometry with respect to the thickness determined by the method (1) from the surface of the A layer side of the laminated film toward the base film direction Asked. The conditions are as follows.
・ Analysis parameter
Analysis beam: Bi ⁺ , negative
Current beam: 1.000pA
Area: 50 × 50μm ²
・ Sputter parameter
Sputter beam ： Cs ⁺ , 10keV
Current beam: 39.000nA
Area: 200 × 200μm ²
In the table, when the total thickness of the A layer is 100%, fluorine atoms by TOF-SIMS in the range of 1% or more and 100% or less in thickness from the A layer side surface of the laminated film toward the base film direction The maximum value of the detected intensity of a and the maximum value of the detected intensity of fluorine atoms by TOF-SIMS in the range from 0% to less than 1% in the thickness from the A layer side surface of the laminated film toward the base film direction. A / b [%] is shown. When this measurement was below the detection limit (when no fluorine atom was detected), “-” was shown in the table.

(5) Self-healing property of layer A According to JIS K5600 (established in 1999) “Scratch hardness (pencil method)”, scratches were formed on the surface of the coating film. The conditions are as follows.

Scratching device: pencil scratch testing machine (KT-VF2391)
Pencil: HB pencil ("Uni" made by Mitsubishi pencil)
Load: 750g
Scratching speed: 10 mm / s
A high-speed camera was installed right above the sample, and the time from when the scratch entered until the brightness difference after 10 seconds of the scratch on the screen became 1.0% or less was taken as the recovery time. The faster the recovery time, the higher the self-healing property. The measurement was performed 3 times and the average value was taken. Moreover, the measurement was performed in a temperature-controlled acrylic box, and was performed at temperatures of 5 ° C., 10 ° C., and 20 ° C. Moreover, the measurement part of the molded film cut out the center part 50mm square of the film, and measured three places in it. The shooting conditions of the camera are as follows.

Light source: LuminalAce LA-150UX ring light installed at the camera tip Camera: VW-6000 (Keyence Corporation)
sample rate: 10pps
exposure time: 20000 μs.

  Those with no wound healing are marked with “-” in the table.

(6) Tg of layer A
It was measured and calculated according to JIS-K-7122 (1987) using differential calorimetry (DSC). The sample of layer A cut out with a blade knife was packed in an aluminum pan and heated from −100 ° C. to 100 ° C. at a rate of 20 ° C./min.
Equipment: “Robot DSC-RDC220” manufactured by Seiko Electronics Industry Co., Ltd.
Data analysis "Disc Session SSC / 5200"
Sample mass: 5 mg.

(7) Contact angle After leaving the sample for 24 hours in an atmosphere at a temperature of 25 ° C. and a relative humidity of 65%, using a contact angle meter CA-D type manufactured by Kyowa Interface Chemical Co., Ltd., distilled water, Nacalai Tesque Co., Ltd. After dropwise addition of diiodomethane, the contact angle after 10 seconds was measured. Each sample was measured three times, and the average value was taken as the contact angle.

(8) Pollution resistance (cosmetics)
Apply 0.5g of “Atrix Hand Cream” manufactured by Kao Co., Ltd. to a sample cut into 5cm square, leave it in an atmosphere of 40 ° C and 95% relative humidity for 6 hours, then 25 ° C and 65% relative humidity atmosphere Leave under for 30 minutes and wipe the surface clean with gauze. After standing for 24 hours in an atmosphere at a temperature of 25 ° C. and a relative humidity of 65%, the surface state was observed and a determination was made according to the following criteria.
○ (excellent): No vitiligo occurred.
● (Good): Almost no vitiligo occurs.
Δ (possible): Vitiligo occurs, but cleans if wiped off.
X (impossible): Vitiligo occurs. Even after wiping, it occurs again after being left for 24 hours in an atmosphere at a temperature of 25 ° C. and a relative humidity of 65%.

(9) Stain resistance (PVC sheet)
Achilles Co., Ltd. PVC sheet “Achilles type C + clear blue tint” is cut into a 4cm square and placed in the center on a sample cut into a 5cm square, and a 500g load is applied evenly under an atmosphere with a temperature of 40 ° C and a relative humidity of 95%. Leave for 6 hours, remove the sample and wipe the surface clean with gauze. The state of the surface was observed and judged according to the following criteria.
○ (excellent): No change in appearance.
Δ (possible): A slight mark is generated at the place where the vinyl chloride sheet is placed.
X (impossible): A clear mark is generated at the place where the PVC sheet is placed.

(10) Molding A three-chamber stretcher (KARO IV, manufactured by Bruckner) was used to grip the edge of the film with a clip, and simultaneous biaxial stretching was performed under the following conditions. At this time, in order to prevent the sample from being detached by the clip, the four sides of the sample are reinforced by sandwiching them with a polyethylene terephthalate film having a width of 10 mm and a thickness of 100 μm. In the stretching by this method, since the laminated film is stretched in the same behavior as actual molding, the obtained film can be regarded as a molded body (molded film). In addition, it is set as a molded film also when not extending | stretching only by preheating. The stretching ratio at the time of molding indicates how many times the film is stretched after stretching relative to the original dimensions.

Film size: 100mm x 100mm
Clip pressure: 5MPa
Preheating / stretching temperature: 100 ° C
Fan air volume: 50%
Preheating time: 40 seconds Stretching speed: 20% / sec.

(11) Molding magnification Cross sections of the laminated film and the molded film are cut with a diamond knife of a microtome (manufactured by Nippon Microtome, RMS-50), deposited with platinum, and then molded with SEM (manufactured by Hitachi, Ltd.). The thickness of the A layer after molding was measured, and the molding magnification was determined from the following formula. The measurement part cut out 50mm square part of the center part of a molded film, and measured three places in it. Since the molding magnification is a change in thickness, it is different from the above-described stretching magnification during molding.

  A layer thickness (before molding) / A layer thickness (after molding).

(12) Moldability After molding, the state of the A layer was visually observed and evaluated according to the following criteria. Moreover, the observation part was performed in the center part 50mm square of a molded film.
○ (good): No cracking or peeling occurs, and there is no problem with surface properties.
X (defect): Cracks and peeling occur and there is a problem in practical use.

Reference Example 1 Preparation of Raw Material A1 <Synthesis of Polysiloxane (a)>
In a 500 ml flask equipped with a stirrer, thermometer, condenser and nitrogen gas inlet tube, 106 parts by mass of ethanol, 270 parts by mass of methyltrimethoxysilane, 23 parts by mass of γ-methacryloxypropylmethyldimethoxysilane, 100 parts by mass of deionized water, 1 part by mass of hydrochloric acid 1 part by mass and 0.1 part by mass of hydroquinone monomethyl ether were charged and reacted at 80 ° C. for 3 hours to synthesize polysiloxane (a). This was adjusted to 50 mass% with methyl isobutyl ketone.

<Synthesis of polydimethylsiloxane block copolymer (a)>
Using the same apparatus as the synthesis of polysiloxane (a), 50 parts by mass of toluene and 50 parts by mass of methyl isobutyl ketone, 20 parts by mass of a polydimethylsiloxane polymer polymerization initiator (WPS Pure Chemicals, VPS-0501) Parts, 18 parts by weight of methyl methacrylate, 38 parts by weight of butyl methacrylate, 23 parts by weight of 2-hydroxyethyl methacrylate, 1 part by weight of methacrylic acid and 0.5 parts by weight of 1-thioglycerin are reacted at 180 ° C. for 8 hours. Thus, a polydimethylsiloxane block copolymer (a) was obtained. The obtained block copolymer had a solid content of 50% by mass.

<Formulation of raw material A1>
75 parts by mass of a polydimethylsiloxane block copolymer (a), 10 parts by mass of the above polysiloxane (a) and 15 parts by mass of a polycaprolactone triol having a hydroxyl group (manufactured by Daicel Chemical Industries, Plaxel 308, molecular weight 850) 15 parts by mass of hexamethylene diisocyanate isocyanurate (Takeda Pharmaceutical Co., Ltd., Takenate D-170N) is added to 100 parts by mass of (mixed), and further diluted with methyl ethyl ketone. A raw material A1 having a solid content concentration of 40% by mass was prepared.

[Example 1]
A solvent prepared by adding 10 parts by mass of 2- (perfluorohexyl) ethyl acrylate and 0.5 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone to raw material A1, and mixing methylethylketone and cyclohexanone in a mass ratio of 93: 7. The solid content concentration is adjusted again to 30% by mass, and the layer A thickness after the aging process is 30 μm on a 100 μm thick polyester base film (manufactured by Toray Industries, Inc., “Lumirror” U46). It applied using a wire bar. After the application, it was heated with a hot air dryer at 100 ° C. for 2 minutes (heating step). Then, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), an ultraviolet ray with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² was irradiated under an oxygen concentration of 0.1 vol%. (Energy ray irradiation process), heating (aging) was performed at 40 ° C. for 14 days (aging process) to obtain a laminated film. Next, the obtained film was molded. At this time, only preheating was performed without stretching.

  Table 1 shows the evaluation results of the obtained laminated film and molded film. Excellent self-healing properties and excellent stain resistance.

[Examples 2-3]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the thickness of the A layer and the ratio of molding stretching were changed. In Example 2, stretching at the time of molding was performed at a magnification of 1.2 times in the vertical direction and 1.2 times in the horizontal direction so that the A layer thickness after the aging process was 23 μm. In Example 3, stretching at the time of molding was performed at a magnification of 1.3 times in the vertical direction and 1.3 times in the horizontal direction so that the A layer thickness after the aging step was 19 μm. The obtained results are shown in Table 1. Even if the thickness of the A layer was reduced, it exhibited excellent self-healing properties and excellent stain resistance. Also, no molding defects were found.

[Example 4]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that 10 parts by mass of 2- (perfluorobutyl) ethyl methacrylate was added instead of 10 parts by mass of 2- (perfluorohexyl) ethyl acrylate. The obtained results are shown in Table 1. Excellent self-healing properties and excellent stain resistance.

[Examples 5 to 6]
A laminated film and a molded film were obtained in the same manner as in Example 4 except that the thickness of the A layer and the ratio of molding stretching were changed. In Example 5, stretching during molding was performed at a magnification of 1.2 times in the vertical direction and 1.2 times in the horizontal direction so that the thickness of the A layer after the aging process was 23 μm. In Example 6, stretching at the time of molding was performed at a magnification of 1.3 times in the vertical direction and 1.3 times in the horizontal direction so that the thickness of the A layer after the aging process was 19 μm. The obtained results are shown in Table 1. Even if the thickness of the A layer was reduced, it exhibited excellent self-healing properties and excellent stain resistance. Also, no molding defects were found.

[Example 7]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that 10 parts by mass of 2- (perfluorohexyl) ethyl methacrylate was added instead of 10 parts by mass of 2- (perfluorohexyl) ethyl acrylate. The obtained results are shown in Table 1. Excellent self-healing properties and excellent stain resistance.

[Examples 8 to 9]
A laminated film and a molded film were obtained in the same manner as in Example 7 except that the thickness of the A layer and the ratio of molding stretching were changed. In Example 8, stretching at the time of molding was performed at a magnification of 1.2 times in the vertical direction and 1.2 times in the horizontal direction so that the A layer thickness after the aging step was 23 μm. In Example 9, stretching at the time of molding was performed at a magnification of 1.3 times in the vertical direction and 1.3 times in the horizontal direction so that the A layer thickness after the aging step was 19 μm. The obtained results are shown in Table 1. Even if the thickness of the A layer was reduced, it exhibited excellent self-healing properties and excellent stain resistance. Also, no molding defects were found.

[Example 10]
10 parts by mass of 2- (perfluorohexyl) ethanol was added to the raw material A1, and the thickness of the A layer after the aging process was 30 μm on a 100 μm thick polyester base film (“Lumirror” U46, manufactured by Toray Industries, Inc.). It applied so that it might become, using a wire bar. After the application, it was heated with a hot air dryer at 160 ° C. for 2 minutes (heating step). Thereafter, heating (aging) was performed at 40 ° C. for 14 days (aging process) to obtain a laminated film. Next, the obtained film was molded. At this time, only preheating was performed without stretching. The obtained results are shown in Table 1.

  Table 1 shows the evaluation results of the obtained film (described as film) and the molded film. Excellent self-healing properties and excellent stain resistance.

[Examples 11 to 12]
A laminated film and a molded film were obtained in the same manner as in Example 10 except that the thickness of the A layer and the ratio of molding stretching were changed. In Example 11, stretching at the time of molding was performed at a magnification of 1.2 times in the vertical direction and 1.2 times in the horizontal direction so that the thickness of the A layer after the aging process was 23 μm. In Example 12, stretching at the time of molding was performed at a magnification of 1.3 times in the vertical direction and 1.3 times in the horizontal direction so that the A layer thickness after the aging step was 19 μm. The obtained results are shown in Table 1. Even if the thickness of the A layer was reduced, it exhibited excellent self-healing properties and excellent stain resistance. Also, no molding defects were found.

[Example 13]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the addition amount of 2- (perfluorohexyl) ethyl acrylate was changed to 3 parts by mass. The obtained results are shown in Table 1. Excellent self-healing properties and excellent stain resistance.

[Examples 14 to 15]
A laminated film and a molded film were obtained in the same manner as in Example 13 except that the thickness of the A layer and the ratio of molding stretching were changed. In Example 14, stretching at the time of molding was performed at a magnification of 1.2 times in the vertical direction and 1.2 times in the horizontal direction so that the thickness of the A layer after the aging process was 23 μm. In Example 15, stretching at the time of molding was performed at a magnification of 1.3 times in the vertical direction and 1.3 times in the horizontal direction so that the A layer thickness after the aging step was 19 μm. The obtained results are shown in Table 1. Even if the thickness of the A layer was reduced, it exhibited excellent self-healing properties and excellent stain resistance. Also, no molding defects were found.

[Example 16]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the addition amount of 2- (perfluorohexyl) ethyl acrylate was 20 parts by mass. The obtained results are shown in Table 1. Excellent self-healing properties and excellent stain resistance.

[Examples 17 to 18]
A laminated film and a molded film were obtained in the same manner as in Example 16 except that the thickness of the A layer and the ratio of molding stretching were changed. In Example 17, stretching at the time of molding was performed at a magnification of 1.2 times in the vertical direction and 1.2 times in the horizontal direction so that the A layer thickness after the aging step was 23 μm. In Example 18, stretching during molding was performed at a magnification of 1.3 times in the vertical direction and 1.3 times in the horizontal direction so that the thickness of the A layer after the aging process was 19 μm. The obtained results are shown in Table 1. Even if the thickness of the A layer was reduced, it exhibited excellent self-healing properties and excellent stain resistance. Also, no molding defects were found.

Reference Example 2 Preparation of Raw Material A2 <Preparation of Raw Material A2>
15 parts by mass of polydimethylsiloxane block copolymer (a) 75 parts by mass, polysiloxane (a) 10 parts by mass and polycaprolactone triol having a hydroxyl group (Placcel 308, weight average molecular weight 850, manufactured by Daicel Chemical Industries, Ltd.) 15 parts by mass of a biuret of hexamethylene diisocyanate (manufactured by Bayer Co., Ltd., Desmodur N3200) is added to 100 parts by mass of the blended (mixed) mixture, further diluted with methyl ethyl ketone, and a solid content concentration of 40 masses % Of raw material A2 was prepared.

[Example 19]
A laminated film was obtained using the raw material A2 under the same conditions as in Example 1. Next, the obtained film was molded in the same manner as in Example 1. Table 1 shows the evaluation results of the obtained film and molded film. Excellent self-healing property even at low temperatures.

[Examples 20 to 21]
A laminated film and a molded film were obtained in the same manner as in Example 19 except that the thickness of the A layer and the ratio of molding stretching were changed. In Example 20, stretching at the time of molding was performed at a magnification of 1.2 times in the vertical direction and 1.2 times in the horizontal direction so that the A layer thickness after the aging step was 23 μm. In Example 21, stretching at the time of molding was performed at a magnification of 1.3 times in the vertical direction and 1.3 times in the horizontal direction so that the A layer thickness after the aging step was 19 μm. The obtained results are shown in Table 1. Even if the thickness of the A layer was reduced, it exhibited excellent self-healing properties and excellent stain resistance. Also, no molding defects were found.

[Example 22]
Polyethylene terephthalate (hereinafter also referred to as PET) [Toray F20S] having an intrinsic viscosity of 0.65 and a melting point of 255 ° C. is used as the polyester resin C, and a polyethylene terephthalate copolymer (cyclohexane) having an intrinsic viscosity of 0.72 as the polyester resin D. PET obtained by copolymerizing 30 mol% of dicarboxylic acid and 20 mol% of spiroglycol component with 0.1 mass% of “Adeka Stub” AS36 (manufactured by ADEKA) as an antioxidant was used. These polyester resin C and polyester resin D were each dried and then supplied to separate extruders.

  Polyester resin C and polyester resin D were each melted at 270 ° C. with an extruder, passed through five FSS type leaf disc filters, and the discharge ratio was polyester resin C / polyester resin D = 1 with a gear pump. While measuring to 2/1, polyester resin C and polyester resin D are alternately laminated by slit plate 1 having 267 slits, slit plate 2 having 269 slits, and slit plate 3 having 267 slits. And it was made to merge by a feed block, and it was set as the laminated body laminated | stacked on 801 layers. The joined polyester resin C and polyester resin D are changed so that the thickness of each layer gradually increases from the surface side to the opposite surface side in the feed block. The polyester resin A has 400 layers and the polyester resin B has 401 layers. It was set as the structure laminated | stacked alternately in the thickness direction which consists of layers. In addition, the slit shape was designed so that the layer thicknesses of the adjacent C layer and D layer were substantially the same. In this design, a reflection band exists between 350 nm and 1200 nm. The laminated body composed of 801 layers thus obtained was supplied to a multi-manifold die, and further, a layer made of polyester resin A supplied from another extruder was formed on the surface layer, and then molded into a sheet shape. It was rapidly cooled and solidified on a casting drum maintained at a surface temperature of 25 ° C. by electrostatic application. The flow path shape and the total discharge amount were set so that the time from when the polyester resin C and the polyester resin D merged to when rapidly solidified on the casting drum was about 8 minutes.

  The obtained cast film was heated with a roll group set at 75 ° C., and then stretched 3.0 times in the longitudinal direction while rapidly heating from both sides of the film with a radiation heater between 100 mm in the stretch section length. Cooled down. Next, this uniaxially stretched film was led to a tenter, preheated with hot air at 100 ° C., and stretched 3.3 times in the transverse direction at a temperature of 110 ° C. The stretched film was directly heat-treated in a tenter with hot air of 235 ° C., then subjected to a relaxation treatment of 5% in the width direction at the same temperature, and then gradually cooled to room temperature and wound up. The thickness of the obtained film was 100 μm. The obtained film was free from delamination and had an excellent gloss tone.

  A layer A was formed on this film in the same manner as in Example 1 to obtain a laminated film and a molded film. The obtained results are shown in Table 1. The resulting film and molded film had excellent metallic appearance and self-healing properties.

[Example 23]
Copolymerized polyester (Eastster PETG6763 manufactured by Eastman Chemical Co., Ltd.) in which 1,4-cyclohexanedimethanol component is 33 mol% copolymerized with glycol component, PET with intrinsic viscosity of 0.65 and melting point of 255 ° C. F20S] was mixed at a mass ratio of 76:24. The mixture was melt kneaded at 280 ° C. using a vented twin screw extruder. As a result, a 1,4-cyclohexanedimethanol 25 mol% copolymerized polyethylene terephthalate resin in which 2 mol% of the by-produced diethylene glycol was copolymerized with respect to the glycol component in the resin was obtained. This is described as 1,4-cyclohexanedimethanol 25 mol% copolymerized polyethylene terephthalate resin (diethylene glycol copolymerization rate 2 mol%).

  PET with intrinsic viscosity of 0.65 and melting point of 255 ° C. [Toray F20S] and 1,4-cyclohexanedimethanol 25 mol% copolymerized polyethylene terephthalate resin (diethylene glycol copolymerization rate 2 mol%) were mixed at a mass ratio of 70:30. . The mixture was dried at 180 ° C. for 4 hours in a vacuum dryer, and after sufficiently removing moisture, supplied to a single screw extruder, melted at 275 ° C., removed foreign matter, and leveled the amount of extrusion, The sheet was discharged from a T-die onto a cooling drum whose temperature was controlled at 25 ° C. At that time, a wire-like electrode having a diameter of 0.1 mm was applied electrostatically and adhered to the cooling drum to obtain an unstretched film.

Then, before stretching in the longitudinal direction, the film temperature is raised with a heating roll, and the preheating temperature is set to 9
The film was stretched 3.2 times in the longitudinal direction at 0 ° C. and a stretching temperature of 95 ° C., and immediately cooled with a metal roll temperature-controlled at 40 ° C.

Next, the film was stretched 3.5 times in the width direction at a preheating temperature of 90 ° C. and a stretching temperature of 100 ° C. with a tenter-type transverse stretching machine, and the temperature was maintained at 210 ° C. for 5 seconds while relaxing 4% in the width direction. Heat treatment was performed to obtain a biaxially oriented polyester film having a film thickness of 188 μm. The obtained biaxially oriented polyester film was very excellent in transparency and moldability although it was slightly weak in scratch resistance.

  A layer A was formed on this biaxially oriented polyester film in the same manner as in Example 1 to obtain a laminated film and a molded film. The obtained results are shown in Table 1. The obtained film and molded film were excellent in self-healing properties.

[Example 24]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the temperature in the heating step was 160 ° C. The obtained results are shown in Table 1. Excellent self-healing properties and excellent stain resistance.

[Example 25]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the solid content concentration was 40% by mass. The obtained results are shown in Table 1. Excellent self-healing properties and excellent stain resistance.

[Example 26]
A laminated film and a molded film were obtained in the same manner as in Example 25 except that the temperature in the heating step was 160 ° C. The obtained results are shown in Table 1. Excellent self-healing properties and excellent stain resistance.

[Example 27]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that methyl ethyl ketone was used for dilution of the raw material A1. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 28]
A laminated film and a molded film were obtained in the same manner as in Example 27 except that the temperature in the heating step was 160 ° C. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 29]
A laminated film and a molded film were obtained in the same manner as in Example 27 except that the solid content concentration was 40% by mass. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 30]
A laminated film and a molded film were obtained in the same manner as in Example 28 except that the solid content concentration was 40% by mass. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 31]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the oxygen concentration in the energy ray irradiation step was 21% by volume. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 32]
A laminated film and a molded film were obtained in the same manner as in Example 31 except that the temperature in the heating step was 160 ° C. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 33]
A laminated film and a molded film were obtained in the same manner as in Example 31 except that the solid content concentration was 40% by mass. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 34]
A laminated film and a molded film were obtained in the same manner as in Example 32 except that the solid content concentration was 40% by mass. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 35]
A laminated film and a molded film were obtained in the same manner as in Example 31 except that methyl ethyl ketone was used for dilution of the raw material A1. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 36]
A laminated film and a molded film were obtained in the same manner as in Example 35 except that the temperature in the heating step was 160 ° C. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 37]
A laminated film and a molded film were obtained in the same manner as in Example 35 except that the solid content concentration was 40% by mass. The obtained results are shown in Table 1. Excellent self-healing property.

[Example 38]
A laminated film and a molded film were obtained in the same manner as in Example 37 except that the temperature in the heating step was 160 ° C. The obtained results are shown in Table 1. Excellent self-healing property.

(Reference Example 3) Preparation of raw material A3 <Preparation of raw material A3>
100 parts by mass of toluene, 50 parts by mass of 2-isocyanatoethyl-2,6-diisocyanate caproate, 59 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Dacel Chemical Industries Plaxel FA1), polycaprolactone-modified hydroxyethyl acrylate (Daicel Chemical) 20 parts by mass of Plaxel FA5) manufactured by Kogyo Co., Ltd. and 0.02 parts by mass of hydroquinone monomethyl ether were mixed, heated to 40 ° C. and held for 12 hours. Thereafter, 82 parts by mass of polycaprolactone triol (manufactured by Daicel Chemical Industries, Plaxel 308, molecular weight 850) was added and maintained at 80 ° C. for 30 minutes, and then 0.02 part by mass of dibutyltin laurate was added and 24 ° C. at 24 ° C. The mixture was held for a period of time, and 111 parts by mass of toluene was added to obtain a urethane acrylate having a solid content of 50% by mass. Then, an active energy ray-curable composition was prepared by mixing 3 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone with 100 parts by mass of this urethane acrylate.

[Example 39]
A solvent in which 10 parts by mass of 2- (perfluorohexyl) ethyl acrylate and 0.5 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone were added to the raw material A3, and methyl ethyl ketone and cyclohexanone were mixed at a mass ratio of 93: 7. The solid content concentration is adjusted again to 30% by mass, and the layer A thickness after the aging process is 30 μm on a 100 μm thick polyester base film (manufactured by Toray Industries, Inc., “Lumirror” U46). It applied using a wire bar. After the application, it was heated with a hot air dryer at 100 ° C. for 2 minutes (heating step). Then, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), an ultraviolet ray with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² was irradiated under an oxygen concentration of 0.1 vol%. (Energy ray irradiation process) A laminated film was obtained. Next, the obtained film was molded. At this time, only preheating was performed without stretching. The obtained results are shown in Table 1.

Table 1 shows the evaluation results of the obtained laminated film and molded film. Excellent self-healing properties and excellent stain resistance.
<Formulation of raw material A4>
100 parts by mass of toluene, 25 parts by mass of methyl-2,6-diisocyanatohexanoate, 11 parts by mass of 2-hydroxyethyl acrylate, 34 parts by mass of polycaprolactone-modified hydroxyethyl acrylate (Dacel Chemical Industries Plaxel FA5) and hydroquinone monomethyl ether 0.02 part by mass was mixed, heated to 40 ° C. and held for 12 hours. Then, 141 parts by weight of polycaprolactone diol (Dacel Chemical Industries Plaxel 220) was added and held at 80 ° C. for 30 minutes, 0.02 parts by weight of dibutyltin laurate was added and held at 80 ° C. for 24 hours, and finally 111 parts by mass of toluene was added to obtain a urethane acrylate having a solid content of 50% by mass. And, 74 parts by mass of this urethane acrylate, 10 parts by mass of triethylene glycol diacrylate (Kyoeisha Chemical Co., Ltd., Light Acrylate 3EG-A), 3 parts by mass of stearyl acrylate (Nippon Yushi Co., Ltd., Bremer SA), 13 parts by mass of toluene and light An active energy ray-curable composition was prepared by mixing 3 parts by mass of an initiator (Irgacure 184 manufactured by Ciba Geigy).

[Example 40]
A laminated film and a molded film were obtained in the same manner as in Example 39 except that the raw material A4 was used. The obtained results are shown in Table 1. Excellent self-healing property.

[Comparative Example 1]
The raw material A1 was applied on a polyester base film having a thickness of 100 μm (“Lumirror” U46, manufactured by Toray Industries, Inc.) using a wire bar so that the A layer thickness after the aging process was 30 μm. After the application, it was heated with a hot air dryer at 160 ° C. for 2 minutes (heating step). Thereafter, heating (aging) was performed at 40 ° C. for 14 days (aging process) to obtain a laminated film. Next, the obtained film was molded. At this time, only preheating was performed without stretching.

  Table 2 shows the evaluation results of the obtained film (described as film) and the molded film. Although excellent self-healing property was exhibited, the contamination resistance was insufficient.

[Comparative Examples 2-3]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the thickness of the A layer and the ratio of molding stretching were changed. In Comparative Example 2, stretching at the time of molding was performed at a magnification of 1.2 times in the vertical direction and 1.2 times in the horizontal direction so that the A layer thickness after the aging process was 23 μm. In Comparative Example 3, stretching at the time of molding was performed at a magnification of 1.3 times in the vertical direction and 1.3 times in the horizontal direction so that the A layer thickness after the aging step was 19 μm. The obtained results are shown in Table 2. Even if the thickness of the A layer was reduced, excellent self-healing property was exhibited and no molding failure was observed, but the contamination resistance was insufficient.

[Comparative Example 4]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the amount of 2- (perfluorohexyl) ethyl acrylate added was 0.1 parts by mass. The obtained results are shown in Table 2. Although excellent self-healing property was exhibited, the contamination resistance was insufficient.

[Comparative Example 5]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that the amount of 2- (perfluorohexyl) ethyl acrylate was changed to 30 parts by mass. The obtained results are shown in Table 2. Although self-healing was insufficient, it showed excellent contamination resistance.

[Comparative Example 6]
A laminated film and a molded film were obtained in the same manner as in Example 10 except that the amount of 2- (perfluorohexyl) ethanol added was 0.1 parts by mass. The obtained results are shown in Table 2. Although excellent self-healing property was exhibited, the contamination resistance was insufficient.

[Comparative Example 7]
A laminated film and a molded film were obtained in the same manner as in Example 10 except that the amount of 2- (perfluorohexyl) ethanol added was changed to 30 parts by mass. The obtained results are shown in Table 2. Although self-healing was insufficient, it showed excellent contamination resistance.

[Comparative Example 8]
A composition containing 5 parts by mass of 1-hydroxy-cyclohexyl-phenyl-ketone is diluted with methyl ethyl ketone to 100 parts by mass of 2- (perfluorohexyl) ethyl acrylate to prepare a coating solution having a solid content concentration of 40% by mass. And this was apply | coated to the laminated film obtained by the comparative example 1 using the wire bar so that the thickness after an energy-beam irradiation process might be set to 1 micrometer. After application, the mixture was heated with a hot air dryer at 80 ° C. for 2 minutes (heating step). Then, using a 160 W / cm high-pressure mercury lamp lamp (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays with an illuminance of 600 W / cm ² and an integrated light amount of 800 mJ / cm ² were irradiated under an oxygen concentration of 0.1% by volume. (Energy ray irradiation process). Next, the obtained film was molded. At this time, only preheating was performed without stretching.

  Table 2 shows the evaluation results of the obtained film (described as a laminated film) and the molded film. Although it did not show self-healing, it showed excellent stain resistance.

[Comparative Example 9]
A laminated film and a molded film were obtained in the same manner as in Example 1 except that 10 parts by mass of hexafluoropropene trimer was added instead of 10 parts by mass of 2- (perfluorohexyl) ethyl acrylate. The obtained results are shown in Table 2. Although excellent self-healing property was exhibited, the contamination resistance was insufficient.

  The laminated film of the present invention can be used in applications where moldability and self-healing properties are required at the same time. In particular, it can be suitably used as a film for decorative molding applied particularly to a housing of a personal computer or a mobile phone.

  The laminated film of the present invention can be formed into a molded body by applying a molding method such as injection molding, pressure molding, vacuum molding, thermoforming, press molding or the like. The laminated film of the present invention can cope with deep drawing.

Claims (11)

A laminated film having an A layer on at least one side of a base film, the A layer having (1) (poly) caprolactone segment and (2) urethane bond, and on the A layer of distilled water contact angle less than 95 ° or 120 °, 87 ° less than der contact angle 70 ° or more in the a layer of diiodomethane in is,
The A layer includes the following component derived from the fluorine compound A (hereinafter referred to as a fluorine compound A-derived component), and 0.5% by mass of the fluorine compound A-derived component in 100% by mass of the total component of the A layer. A laminated film comprising 25% by mass or less .
Fluorine compound A: refers to a compound represented by the following general formula (1).
B—R ¹ —R ^f —General formula (1)
(B in the above general formula represents a reactive site or a hydroxyl group, R ¹ represents an alkylene group having 1 to 3 carbon atoms and an ester structure derived therefrom, R ^f represents a fluoroalkyl group, You may have chains in the structure.) 2. The laminated film according to claim 1, wherein a contact angle of the diiodomethane on the A layer is 80 ° or more and less than 87 °. The laminated film according to claim 1 or 2, wherein the A layer has (3) a polysiloxane segment and / or a polydimethylsiloxane segment. When the total number of fluorine atoms, carbon atoms, nitrogen atoms, oxygen atoms and silicon atoms detected by XPS on the surface of the layer A side of the laminated film is 100%, the number of fluorine atoms is 0.4% or more and 50 % Or less, The laminated film according to any one of claims 1 to 3. When the total thickness of the A layer is 100%, the detection intensity of fluorine atoms by TOF-SIMS is in the range of 1% to 100% in thickness from the A layer side surface of the laminated film toward the base film direction. When the maximum value is a, and the maximum value of the fluorine atom detection intensity by TOF-SIMS in the range of 0% or more and less than 1% in the thickness direction from the A layer side surface of the laminated film toward the base film direction is b. A / b is 0% or more and 60% or less, The laminated film according to any one of claims 1 to 4. The laminated film according to claim 5, wherein the a / b is 5% or more and 20% or less. Tg of the said A layer is -30 degreeC or more and 15 degrees C or less, The laminated | multilayer film in any one of Claims 1-6 characterized by the above-mentioned. The laminated film according to any one of claims 1 to 7, wherein the layer on at least one side of the base film is composed of only one A layer. The laminated film according to any one of claims 1 to 8, wherein the average breaking elongation of the A layer at 80 ° C and 150 ° C is 65% or more and less than 100%. The touch panel comprising the laminate film according to any one of claims 1-9. Molded body comprising a laminated film according to any one of claims 1-9.